Method and apparatus for catalytic processes



June 19, 1945. Y w Q 'EDMISTR 2,378,542

METHOD AND APPARATUS FOR CATALYTIC PROCESSES H0 lydracarad Vig/vors Maz Qdm June -19,

W. C. EDMISTER METHOD AND APPARATUS FOR CATLYTIC 'PROCESSES Filed Aug. 50, 1941 2 Sheets-Sheet 2 Ileana y Ma 9.2M...

'Mr/leg Patented June-119, 1945 l PARATUS Foa caramrrrc` rizocrzssns` '.-Wayne CfEdmister, Flossmoorflll., assignor'to'A 'l Standard Oil Company, Chicago, loll., a, com;

ration oflmliana e ,y Application August 3o, 1941 serial No. 409,071

' 11` claims. "(cl. 19e-s2)- invention pertains to afcatalytic hydrocarbon conversion system and it relates more par# ticularly to improvements in processes and apparatusefor handling uentcatalyst in aso-called Subsequently the catalyst :and reaction products. can be separated -and the catalystrecycled to a reaction zone or regenerated. 'I'he spent catalyst can be regenerated by suspending it in a gas mixlture in which case the regenerated catalyst and regenerationfgases must befseparated before'the.

catalyst isreturned tothereaction zone. In such systems the fluent solid catalyst can be pneufluid-type hydrocarbon catalytic conversion sys. *teni l In the iluid-type catalyticconversion system'a powdered or granulated catalytic vmaterialeects; c'onversion--wh'ilel the catalyst isvsuspended in the gases or vapors undergoingv reaction.

provide a systemA whereinl gases for vapors are employed to return cycloneseparated catalyst to the system. Still another objectof my invention l separators are mounted in matically conveyed to highlevels and passed *through standpipes, dipflegs,Y or other conduits from high levels to low levels and from zones of relatively greater or lower-pressure.` If there is any Vinterruption in this Ailow of separated solids in a conduit there is a tendency of the solids to bridge and thereby cause a plugging of the conprovide `improved methods and means for recovering finely divided catalyst particles fromv gases or vapors 'from a reaction or regeneration zone and for returning the separated catalyst to the system. In

- f the recovery of powdered catalyst'from reaction gases orr regeneration gases bya system of cyclone sarily `be a pressure drop' across each stage;` an object of my invention is to provide improved method and means for effecting 'the desired operating vpressures in these various stages and to .secure positive operation'of each lcyclone separator in the system. A furtherobject is to provide improved methods kand means.` yfor increasing the eiliciency of a multil-stage cyclonesystem. A still iurtheobject is to provide `improved methods and meansfor making cyclone separator dip legs accessibleand for'obtaining access to valves for controlling the operation of each cyclone sepa.-

rator. i y Afurther object is to'provideimproved methods and-means i'ory admiring the recovered fine cata- -lystfparticles with coarse catalyst particles separated within the reaction or regeneration zones by settling or othermeans. Another object is to duit.; Anobject ofinyinven'tionfistoprovide. y method and apparatus-21er effecting thedesired v.flow of lfiuentli'solidacatalystand; prevent such vcatalystbridging iorl'plugging.' v 1 f A furthe'robject4 of lm'yin'vention isto l separators operating instages there lmust neces= 1 is to provide a-system wherein these gases -.or

'vapors can also function to effect anfadmixturle of catalyst iines with 'coarser catalyst andv to eiIe'ct vastripping or purging'of bothne and coarse hopper into an outside collecting hopper or hoppers.. Steam ,for aerating catalyst lin thedipleg may be introduced into the dip .leg at an accessible point outside the main hopper and likewise l readily accessible.

an exposed control valve is Catalyst `from thel exterior collection hopper or hoppersfmaybe injected into' thel interior main hopper. Likewise the catalystmay be injected intothe dense phaSeorcoarse-'catalyst recovered vfrom lthe reactor orggre'generator icy-means of steam. This steam maycserve as the stripping Vand aerating4 gasv for freeing spentandiregenerated catalyst from,1 vapors-and gases. By injecting the -cyc'lone separated catalyst into `the settled or dense phase catalyst.. itis transferred therewith. Y o Y In accordance .with my present invention, `the cyclone' dip legs deliver `the v recovered ycatalyst to a collector hopperoryhoppers external tothe reactoror,regenerator.. I'maintain a substantially constant pressure in said hopper or hoppersy which preferably is not substantially greater than the pressure in the interionmain hoppen The lmaintenanceof a constant pressure inthe collect hopper. which can suitably be doughnut-shaped.

vlating catalyst transfertherefrom. f, v 1 These external hoppers maybe in theform of tor hopper is essential bothvfrom'the standpoint of regulating catalyst discharge thereto from the cyclonezdip legs and from'the standpoint of regua multiplictyof hoppers, one foreach set of cyclones; orthe dip legs can deliver to a common and inclined :from 'which the recovered catalyst can be withdrawn. In one embodimentfour sets of three-stage .cyclones can be used. It is contemplated, however, that when desired a set may Vcomprise a common tertiarycyclone for each of two parallel groups of cyclones vcomposed of primary and secondary units.

Recovered catalyst can be transferred from the hopper or hoppers either to the interior main hopper, directly to the same or another reactor or regenerator, or injected into a settled or dense phase being transferred. The invention will be more clearly understoodsfrom thefollowing detailed description taken with the accompanying drawings illustrating the invention and forming a part of the specification. Referring to the drawings: Figure 1 is a schematic flow .diagram illustrating a modification of the invention employing a common external annular collector hopper; w

Figure 2 is atop View showing the'arrangement of cyclone separators of Figure l; and

Figure 3 isa schematic flow diagram showing one embodiment of my invention as vappliedto a catalytic cracking system employing a plurality er external collector hoppers and aninternal amnilar catalyst settling zone. l

All of the figures are diagrammatic. Correspending parts of the several figures are designated by like reference numerals.

Although my invention is applicable to a wider variety of catalytic conversion systems it is primarily` designed for hydrocarbon conversion processes such as alkylation, aromatization, dehydrogenation, desulfurization, gas reversion, hydrocarbon synthesis, as for example from natural vgas or coal, hydrogenation, isoforming. isomerization, polymerization, reforming, etc., and it is particularly applicable tothe catalytic cracking of gas oil and reduced crude for the production of high antiknock motor fuels. The

ture can be prepared by ball-milling siliui'lyd drogel with alumina or magnesia, dryirfgthe re'- sulting dough at a temperature of about 240 F.

. and then activating by heating to a temperature of between about 900 F. and about 1000o F. The catalyst per se forms no part of the present invention and it is, therefore, unnecessary to describe it in further detail.

When using powdered catalyst having a particle size of between about 1 and about 100 microns, I prefer to employ vapor velocities in the reactor of between about 0.4 and about 4 feet per secondffor example about 1,-5 or 2 feet per second. Theca-talyst-to-oil weight ratio for catalytic vcracking can be between about 1:1 and about :1 and is preferably about 3 or 4 to l. The catalyst residence time may range from a few seconds to an hour or more, for example it may be about 4 to 10 minutes. The Vapor residence time is usually about 10 to 30 seconds. The temperature prevailing. throughout the reactor may be maintained at about 900 F. to about charging stock may consist of ormay contain.

hydrocarbons produced or recovered from other conversion process, hydrocarbons produced by a carbon monoxide-hydrogen synthesis, distillate from high pressure wells, or the like. In the illustrative embodiment I will describe the invention as applied to the catalytic cracking of Mid- Continent gas oil.

The feed stock is vaporized and heated, for example in conventional pipe still furnace (not shown), to a temperature of :between about 800 F. and about 1050 F., for example about 900 F., and is introduced at a pressure :between about atmospheric and'about 50 pounds per square inch, for example about 15 pounds per square inch, through transfer line I0 to the bottom of reactor II. Varying quantities of steam, i`. e., between about-2% and about 20% by weight, can be included with the hot vapors introduced to the transfer line;v vapors. in transfer line I0 pick-upQpowdered catalyst from base ofstandpipe .I2 inamounts regulated by valve. I3. and `carry the catalyst intoreactor .I I. p sure at the base of 'standpipe I2 should' be be tween about 1 and about 5 pounds per square inch higher than the 4pressure in transfer line .IIL The catalyst in standpipe I2 is maintained'in fluent condition by aeration steam introduced through line I4.

Reactor I I shouldbe of such sizeand shape as to effect contact of the vapors with the desired amount of catalyst for the required period of time. Catalysts adapted to my process are, for example ofthe silica-alumina or silica-magnesia type. The catalyst can be prepared by the acid treating of natural clays such as bentonite or by synthetically preparing a powdered. silica-alumina or silica-magnesia mixture. Such a mix-A The catalyst in this specific example is in powder form with a particle size of between about 1 and about 100 microns, i. e., with about 50% of the catalyst passing a 400- esh screen. The inyentionis applicable, however, to other' rcatalyst sites provided only that the catalyst is such size andv density that it can be aerated and handled a fluid in the manner herein described. Higher Vgas or vapor velocities may be required for coarser catalyst particles but these particles can be of such size as to be retained on a 400, 300, 2.00, 100, or even E50-mesh screen.

The density of the catalyst particles per se may .be as high as 160 pounds per cubic foot, but the bulk density of the catalyst which has settled for five or ten'minutes will usually be from about 35 to about pounds per cubic foot. With slight aeration, i. e. with. vapor velocities of between about 0.05 and about. 0.5 feet per second, the-bulk density of 1 to 100- mcron catalyst will be between about 20 and about 30 pounds per cubic foot. With vapor velocities of between; about 1 and about 3 feet 'per second .the catalysteis in the .dense turbulent suspended catalyst phase and thebulk density of such catalystrnay be between about 10 and about 20 pounds, for exam#y ple about 15 to 18 pounds per cubic foot. With higher ,vapor velocities, i. e., the Vapor velocities existing in transfer lines,` the catalyst is. in adivlute dispersed phase, the density of which may .ably'is at least 12 pounds per cubic foot lighter than the dense turbulent suspendedcatalyst phase. This latterphase is at least 1, preferably ..at least pounds per cubic foot lighter than the .aerated catalyst being transferred-to the dense The bulk density of the aerated catalyst phase or the dense turbulent suspended catalysty phase is greater in the absence of appreciable catalyst fmes than in the presence of substantial amounts of such fines. When the recovered catalyst consists almost entirely of fines, as exemplified by catalyst particles separated from the dilute phase by cyclones, 'the bulk density of settled or lighter aerated catalyst may be only l0 or l5 pounds per cubic foot.

lys't within the reactor in the dense, turbulent susf pended catalyst phase` tend upwardly into'main hopper I5 as'shown in Figuref3, so that the annular space between the The-,reactor II may ex.-

walls of the reactor `I I and the Walls of the hopper I will provide `an accumulation/zone for settled catalyst, If desired, the diameter of the reactor rnay be narrowed atL its upperen'd, When y the reactor. is not restricted,v however, the ycatalyst can flow 'directly fromthe reactor I I tothe stand'- pipe I6 as 'shown in Figu-ie l, or to the annular accumulation v,zone I1 of Figure 3 and thence to standpipe I5a. withoutthe bulk o'f the [catalyst passing from the dense Vto the dilute phase. .Any catalyst.' particles which remain suspended ,in the dilute'phase kare recovered by means of cyclone separators.

'I'he enlarged main hopper I5 is connected to the reactor .by outwardly and upwardlyextending wall I8, forming the bottom of the hopper. .Inside the hopper I5 and around 4the periphery thereof I provide a plurality of cyclone separators.

' I may employ one, two, three or more kstages of cyclone separators in each set and I may have two or moreparallel sets. The dip legs from each of the cyclones `extend through the base ofthe eny larged main hopper I5 to collector hopper or hoppers whereby controlv valves and aeration ports areexterior of the reactor and main hopper a'nd therefore easily accessible.

` Gasand catalyst fines from the upper part of the hopper I5 maybepicked up by one or` more lines I9 ata pressure. o f about 8 pounds1 per square inchand conductedeto primary cyclones 20,

'There is a vpressure drop through each of the primary cyclones and v-each of fthe succeeding stages so that gases may leave vcyclones '2li through line 2I to secondary cyclones 22, lines -23 and tertiary cyclones 24, Each of the cyclones has its'respective dip leg 25 `which passes substantially vertically downward 'through the base vof hopper I5 and which has an externall regulating vvalve 26 near its base. ,Aeration steam ,may be introducedintc each dip legby. ports 2'I`at a point above the respective external valves 26 for' maintaining thesettled catalystin the dip V'leg in aerated condition. y j l Referring more particularly to Figures 1 and 2,

I contemplate the use of ,a common tertiary cyclone 24 for eachlof twoparallelgroups of cyclones composed of primary andfsecondary units ygiving a total'ofy ten dip legos'l 25 delivering to a common annular hopperwhichis inclined and discharges the vrecovered catalyst into'standpipe 29. Aeration steam maybe introduced into collector standpipe 29 for maintaining the settled catalyst in aerated condition. V, Likewise, the collection hopper or hoppers can be aerated to insure complete delivery oi'r Vcatalysttherefrom. Line 3 0 communicates with the dilute: phase in hopper` I5 `or with discharge 4conduit 3|, thus assuring flow of catalyst -into collector hopper 2 8.

Y `car the base of standpipe 29, aerating steaminrlet 32 and regulating valye 3 3` may 'be'provided.-

If desired the standpipes`28 and I 6 may be merged .,.ncar the top of I6, Stean from line'34 picks up catalyst fromthe base ofY standpipe v29 and intro- 'duces this-catalyst into main standpipe' I6 in fwhich'spent catalyst is being transferred or into the same or a different reactor or regenerator.

n The Steam Whicli is vthusintroduced into the main standpipe v29 serves-to admixthe catalyst fines with the coarsercatalyst particles and to effect a degree of stripping of hydrocarbon vapors from both the finev and coarse catalyst in the standpipe I I6. Additional stripping gas may be introduced.

for example by lines Aand 35. v With. reference to Figure 3, thefdiplegs of each set of cyclones discharge intoa separate collection hopper l1. I'he dip legs may be run' 39, regulating valve 4I) anda. steam line 4I for can be returned to the reactor IIby line '12.`

returning the"'catalyst to the upper hopper I5 by line 42. Alternatively' the recovered catalyst can be injected intothe same or different reactorI and/or regenerator. 'I'hus the cyclone separated catalyst 'I'he recovered catalyst fines may be injected into the regenerator at an intermediate or upper point. Likewise, it may be injected by line 'II fintor the standpipe I Bor 16a transferring the spent catalyst to the regenerator 43. The steam which is introduced by lines 42 with recycle catalyst will furnish the necessary aeration 'and stripping steam for the main hopper I 5. I can, of course, introduce additional aeration or stripping steam into hopperl I5 'by conventionalf means. For example, steam ymay be supplied near the base of the annular settling zone of the reactor or regenerator by lines 44 and 45. Therate of injection of carrier steam Vthrough lines 4I or the adjustment of valves `40 maybe automatically controlled in' accordance with the pressuringhead inthe standpipesl for insuring smooth and continuous catalyst discharge therefrom.

The vapors are withdrawn from the separation zone through line 48 to a suitable fractionation and 'recovery system (not shown). The product fractionation .forms no part of the present invention and it will not be described in detail. lI

prefer,' however, to

leil'ect the fractionation.. of

the heavier products at a. relatively low pressure,

as for example about 5 pounds per square inch. Any unrecovered catalyst may be recycled` with the heaviest condensate with fresh feed. The overhead from this initial fractionation is preferably cooled to condense and separate'water. The remaining hydrocarbons` can then be fractionated at high' pressure. between about 100 pounds perA square inch and about pounds per square inch in any suitable arrangement of fractionators, absorbers, stabilizers,` etc., to obtain the desired sas and gasoline fractions.,

Spent catalyst is withdrawn by standpipe IB or Iia which is` aerat'ed by steam introduced by line SII .immediately above control valve 4,1.

Catalystis picked up from the base of this standpipe by air Aintroduced through line 48 and is carried thereby vinto regeneration chamber 4! which is'similarl to conversion reactor II although it may be larger in size, Drticularly if temperature control is'elfected by recycling/regenerated l catalyst through a cooler 49 or 49a and back'to the regenerator 43. The regenerator can be suitably designed fora vertical gas velocity'of between about 0.4 and about 4.0 feet per` second, preferably about 2 feet per second. so that a dense turbulent suspended catalyst pbase is maintained therein. `The regenerator is superimposed by catalyst can be irected into the same or different lyst.

Any catalyst particles which remain suspended n in the dilute phase are removed therefrom by means of cyclone separators mounted inside the main hopper 50 and around the periphery thereof, arranged in a manner similar to that described in connection with the reactors. Thus regeneration gases enter primary cyclone 5I through'line 52i The gases from primary cyclone 5l are introduced through line 53 to secondary cyclone 54 and thence'to the tertiary cyclone 55. Any number of stages can be used. The final regeneration gases are withdrawn' through line 56 and residual catalyst fines may be removed from regeneration gas by an electric precipitator. Separated catalyst from the cyclones passes through the respective dip legs 51A which extend through the bottom of hopper 50 and are provided with external operating valves 58 and aerationports 59. The dip legs 51 discharge into collection hoppers 60 or 6I which are the counterpart of the collection hoppers 31 and 28 respectively, previously described 'in connection with the recovery of spent catalyst from the reactors. Thus the dip legs may be run into the hoppers directly or may join and enter hoppers by means of a common gathering line. Likewise, the dip legs of the primary and secondary cyclones canjoin the dip leg of the tertiary cyclone which in turn discharges vertically into the hopper. If desired the dip legs 51 of each set of cyclones discharge yinto a separate collection hopper 60. 4 The hopper standpipes 62 and 63 are provided at their base with an aerating s'team inlet 64, regulating valve 65, and a steam line 66 or I4, respectively. In Figure' 3 the catalyst is illustrated as returning to the main hopper 5|) by line Alternatively, the recovered regenerated regenerator and/or` reactor. Likewise, the recovered catalyst lines may be injected into the dense catalyst iiowing through cooler 49a. It is also contemplated as shown in Figure l that the recovered catalyst may be injected into the standpipe l2 transferring the regenerated catalyst to the reactor I l. Generally the flow of the catalyst described in connection with the reactor finds its counterpart inthe regeneration stage.

Temperature control in the regenerator may be effected by withdrawing dense phase regenerated catalyst from the regenerator, passing it through a cooler 49 or 49a and reintroducing it at the base of the regenerator. The cooler can be a heat exchanger comprising vertical tubes andshell. The aerated catalyst preferably passes through the tubes. Water or other heat transfer fluid maybe introduced into the shell and hot fluids such as steam withdrawn. The level of the liquid phase in the shell can be controlled to regulate vthe extent of heat exchange. Alternatively, Sterling-type boiler tubes may be mounted within the regenerator and around the periphery thereof.

The aeration steam is withdrawn from the collector hopper or hoppers 60 or 6| through line 68 and it may be vented through line 69 into the dilute phase o' the main hopper 50 or through line 10 to the conduit 56 withdrawing the gases from the regenerator 43. The introduction through line 69 offers the advantage of providing for the recovery of any suspended solids in the steam and venting .to the conduitk 56 assures better pressure control. A slightly higher pressure is maintained in the collection hoppers then in the main hopper or in the gas or vapor discharge conduit. y

Although I have described steam for positively discharging catalyst from dip legs and standpipes it should be understood that mechanical pumps such as Fuller-Kenyon screws or other means than pneumatic can be used in transferring talyst.

From'the above description other modifications and operating conditions will be apparent to those skilled in the art. Therefore, while I have described inrdetail certain examples of my invention, it should be understood that my invention is not specific to the particular modifications or operating conditions set forth but is defined by the claims.

1. In an apparatus for catalytic conversion, a contacting chamber, an enlarged separation chamber above said contacting chamber, a plurality of cyclone separators in said separating chamber, means for accumulating and transferring settled catalyst from said contacting chamber, exterior catalyst collection means, conduit means for transferring cyclone separated catalyst into the collection means exterior of said contacting and separating chambers, and means for impelling said cyclone separated catalyst from said exterior collection means into said means for accumulating and withdrawing settled catalyst.

2. In acatalytic conversion system comprising a vertical contacting chamber, means for introducing catalyst and gases into said contacting chamber whereby a dense turbulent suspended catalyst phase may be maintained therein, a separation chamber superimposed above said contacting chamber, and cyclone separators within said separation chamber, the improvement comprising catalyst conduit means extending downwardly from said cyclone separators to a point exterior of said separation chambenmeans for discharging catalyst from Said downwardlir extending catalyst conduit means into external collection means, and pressuring means for conveying the separated catalyst from said external collection means to a point in said catalyst conversion system wherein catalyst is maintained in a dense phase.

3. The apparatus of claim 2 wherein said separation zone is an enlarged chamber having a laterally extending wall between the contacting zone and the separation chamber, and each of said catalyst conduit means extending substantially vertically through said laterally extending wall.

4. The apparatus of claim 2 which includes a laterally extending wall vbetween said contacting zone and said separation chamber, a pair of primary and secondary cyclone separators in said separation chamber, means for introducing gases from said cyclone separators to a common ter- Vhopper at a point below Vtalyst therein. j

` of said chamber. to a point outside of said cham,

ber into an exterior collection hopper, a standpipe extending from said exterior hopper, positive catalyst transfer means at the baseV of said standpipe, and means Vfor 'introducing catalyst` from the base of the standpipe to said internal the levelof settled ca- 6. ,'I'he'apparatus of claim 2`which includes an annular catalyst receiver and means for maintaining a substantially constantl pressure in tling zone.

said receiver slightly in excess of that maintained in the settling chamber.

7. 'In a catalytic conversion system of the type wherein agas or vapor passes upwardly in a contacting zone and is contacted in said zone with a dense turbulent suspended catalyst phase, wherein the Vbulk of the catalyst is removed from gases Aand vapors in anv enlarged settling zone and wherein residual catalyst material is removed from'gases or vapors by means of cyclone sep# arators, the method of combining cyclone separated catalyst with settled Vcatalyst which comprises discharging said cyclone separated catalyst'v intoan external collection hopper and positively impelling cyclone separated catalyst into said set-V 8. Thel methodk of claimA k.7 wherein a Vbody of settled catalyst is maintained in the lower part of the settling zone and wherein the removed catalyst nes `fare. introduced into the bed of settled r9. The metrica or claim v wherein cataiyst aries 5 removed'from the settling zone immediately fol-` lowing one contacting zone is returned to the system by introducing it directly into a contacting zone.

10. In a catalytic hydrocarbon conversion system wherein hydrocarbon vapors pass upwardly through a reaction zone in contact with a dense turbulent suspended catalyst phase and thence to an enlarged catalyst settling zone wherein spent catalyst from said settling zone is thenv transferredito 'a regeneration zone and contacted with regeneration gases flowing upwardly therein at such a velocity as to maintain the catalyst in a dense turbulent suspended catalyst phase,

wherein gases from the regeneration zone pass to an enlarged settling zone from which catalyst is" transferred to the conversion .zone and wherein catalyst fines are separatedv from gases and vapors leaving said respective settling zones, the method of returning said catalyst ilnes to the system which comprises discharging said nes from a point Within each settling zone to a hopper exfterior of the respective contacting zones and settling zones, and positively injecting said iines by means of steam into the settled catalyst owing from said respective contacting zones whereby the impelling steam effects aeration and stripping of the settled catalyst.

11. In a catalytic conversion system of the type wherein a gas or vapor passes upwardly in a contacting chamber and is contacted in said chamber with a dense turbulent suspended catalyst phase, wherein thebulk of the catalyst isremoved from gases or vapors in an enlargedv settling chamber and wherein residual catalyst materialA is removedfrom gases or vapors by means of cyclone separators. the method `of combiningj cyclone separated catalyst with settled catalyst which comprises introducing cyclone separated catalyst into an Yexternal catalysty collection chamber and positively impelling cyclones/ep arated catalyst from said collection chamber into a chamber within the catalytic conversion system containing a body of settled catalyst.

WAYNE C. EDMISTER. 

